CN103626721B - A kind of method of coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether - Google Patents
A kind of method of coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether Download PDFInfo
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- CN103626721B CN103626721B CN201210307914.3A CN201210307914A CN103626721B CN 103626721 B CN103626721 B CN 103626721B CN 201210307914 A CN201210307914 A CN 201210307914A CN 103626721 B CN103626721 B CN 103626721B
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/027—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring
- C07D295/03—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements containing only one hetero ring with the ring nitrogen atoms directly attached to acyclic carbon atoms
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C213/00—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton
- C07C213/02—Preparation of compounds containing amino and hydroxy, amino and etherified hydroxy or amino and esterified hydroxy groups bound to the same carbon skeleton by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07D—HETEROCYCLIC COMPOUNDS
- C07D295/00—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms
- C07D295/02—Heterocyclic compounds containing polymethylene-imine rings with at least five ring members, 3-azabicyclo [3.2.2] nonane, piperazine, morpholine or thiomorpholine rings, having only hydrogen atoms directly attached to the ring carbon atoms containing only hydrogen and carbon atoms in addition to the ring hetero elements
- C07D295/023—Preparation; Separation; Stabilisation; Use of additives
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- Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
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Abstract
The present invention relates to a kind of method of coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether, comprising: the mixture of Monomethylamine, dimethylamine and Trimethylamine 99 and two (2-halogenated ethyl) ether are reacted at least 2h by (1) between 30 DEG C ~ 100 DEG C; (2) product step (1) obtained and polyethylene polyamine react at least 3h between 100 DEG C ~ 180 DEG C.The methylamine mixture that the present invention can utilize methyl alcohol and ammonia directly to synthesize comes coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether, do not need to be separated into Monomethylamine, dimethylamine and Trimethylamine 99, decrease the sepn process of mixing methylamine, both decrease facility investment, also save production cost and resource simultaneously.
Description
Technical field
The present invention relates to a kind of method of coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether.
Background technology
N-methylmorpholine is a kind of heterocyclic tertiary amines, it is a kind of important fine chemical material, it can be used as the catalyzer of polyurethane foam production and the catalyzer of medicine synthesis and organic synthesis, also can be used for synthesizing medicine, agricultural chemicals, tensio-active agent, emulsifying agent, corrosion inhibitor, the fine chemical products such as N-methyl morpholine oxide (NMMO), also can be used as solvent, extraction agent and polyurethane coating curing agent.Therefore research and develop N-methylmorpholine new synthetic process extremely important, there are good market outlook.
Current world N-methylmorpholine production equipment mainly concentrates on several countries such as the U.S., Japan, Germany, and also there is part producing device in China.The production method of N-methylmorpholine mainly contains following several synthesis technique: (1) morpholine methyl method, and 1. morpholine and methyl alcohol carry out alkylation, and catalyzer is SiO
2-H
3pO
4, catalyst specific surface is 400m
2/ g, morpholine: methyl alcohol is 40: 60, take flow velocity as the catalyst fluidized bed that the mixing steam of 106g/h passes into 200ml, at 160 DEG C, reaction can obtain 91%N-methylmorpholine, morpholine transformation efficiency is 95%, catalyst particle size is 60 ~ 200 orders, (German patent DE 2205597A1,1973); 2. adopt morpholine and methyl chloride to obtain N-methylmorpholine as raw material, both mol ratio are 1: 0.3 ~ 0.4, and temperature of reaction is 5 ~ 15 DEG C, reaction medium pH value is 12.5 ~ 14.0, this method yield is higher, technique simple, (russian patent SU1164234,1985); 3. morpholine, methyl chloride and water or alkali aqueous solution is adopted to prepare N-methylmorpholine, morpholine 3700 parts mixes at 60 ~ 65 DEG C with 2000 parts of water, add 1000 parts of methyl chlorides again and 1750 parts of 50%NaOH aqueous solution react, then component distillation, obtain the azeotropic mixture of N-methylmorpholine and water, this mixture to obtain N-methylmorpholine 1854 parts altogether after dewatering further and refining, and yield is 43.7%(DE3504899, and 1986); (2) Diethylene Glycol method, the proportioning (molecular ratio) of raw material methylamine and Diethylene Glycol is 1 ~ 3 ︰ 1, under the katalysis of hydrogen and nickel series hydrogenating catalyst, temperature of reaction is 200 ~ 250 DEG C, pressure is 1.0 ~ 10.0MPa normal atmosphere, reaction product obtains product through fractionation by distillation, and productive rate is 60 ~ 90% (US3709881,1973); (3) diethanolamine method, diethanolamine and methyl-sulfate react at 105 ~ 200 DEG C, use active oxidation Calcium treatment, decomposition of methyl product and neutralisation of sulphuric acid radical ion, the N-methylmorpholine obtained, yield reaches 81 ~ 95%, and this method yield is higher, but last handling process is more complicated, there is not yet industrialization report.(US3087928,1963; SU793978,1981); (4) dichloroethyl ether method, dichloroethyl ether reacts with methylamine under the existence of 110 DEG C and alkali, and can obtain N-methylmorpholine, yield is about 50%, simultaneously by product dme.Dichloroethyl ether can produce the by product of oxyethane from chlorohydrination, price is not high, but resource-constrained, this method yield low (US3155656,1964); (5) methylcarbonate and morpholine method, the N-methylmorpholine that utilizes methylcarbonate and morpholine to be Material synthesis, reaction process condition is: material proportion is n (C
4h
8nO): n (C
3h
6o
3)=1: 1.2, the reaction times is 3h, and temperature of reaction is 100 DEG C, and yield can reach more than 95% people such as (, chemistry and bonding, 2007, N-methylmorpholine green synthesis method) Yu Hongyan; (6) N,N-Dibenzylamine is the synthetic method of raw material, and react with 2,2 '-N,N-Dibenzylamine and trolamine and can prepare N-2-hydroxyethyl morpholine, similar also can prepare N-methylmorpholine.Catalyzer is SiO
2-2Al
2o
3, specific surface 550 ~ 700m
2/ g, temperature of reaction 240 DEG C (DE2624016,1976); (7) dianhydride alcohol, liquefied ammonia, methylamine method coproduction N-methylmorpholine and morpholine: it is with dianhydride alcohol, liquefied ammonia, Monomethylamine for raw material, at hydrogen and Ni-Cu-Al
2o
3-MgO, Ni-Cu-Al
2o
3under the catalyzer such as-BaO exist, will add from fixed-bed reactor top continuously after material gasification, reaction pressure is 1.0 ~ 2.5MPa, and temperature of reaction is 190 ~ 260 DEG C.This method reaction process is complicated, and used catalyst is more, and industrialization is more difficult, (CN1911505,2007, Tian Zhensheng, Zhang Jibo etc.).
In the preparation method of above-mentioned N-methylmorpholine, or product yield is lower; Or processing condition are harsh, need use catalyzer, equipment requirements high; Or adopt a large amount of alkali lye to be raw material, equipment corrosion is serious, to operator and environment, there is very large potential hazard.Constantly perfect with environmental regulation along with environmental consciousness improves constantly, require chemical industry not use as far as possible or use raw material environment and the person being had to harm less, therefore need to research and develop a kind of reaction conditions gentle, product yield and purity high, and the N-methylmorpholine preparation method of more environmental protection.
Two (2-dimethylaminoethyl) ether is that it is a kind of important tertiary amine catalyst, and its chemical structural formula is in yellowish oily liquids
sterling is colourless liquid, boiling point 190 DEG C.It is the urethane amines catalyst that a kind of people are familiar with, and as far back as the end of the sixties, started development abroad, oneself is widely used in the production of the polyurethane flexible foam of high resilience and cold-curing at present.
Two (2-dimethylaminoethyl) ether has multiple synthetic method, and in these synthetic methods, (1) is had to utilize N, N '-Dimethylaminoethoxy sodium and N, N '-dimethyl thanomin is under the effect of chlorination sulfone, obtain two (2-dimethylaminoethyl) ether at 115 DEG C of reaction 2.5h, productive rate is 54% ~ 57%(US4177212,1979); (2) utilize N, N '-Dimethylaminoethoxy sodium and N, N '-dimethyl thanomin is under the effect of sulphur trioxide, and obtain two (2-dimethylaminoethyl) ether at 115 DEG C of reaction 2.5h, productive rate is 63% ~ 68%(US4247482, and 1981); (3) N is utilized, N '-dimethyl thanomin is at 200 DEG C ~ 450 DEG C, by assorted many solid acid catalysts under gas phase condition, heteropolyacid solid catalyst used is aluminum oxide, modifies aluminum oxide, silicon titanium, sial, borophosphoric acid ester, under the effect of diatomite etc., obtain two (2-dimethylaminoethyl) ether (US4474988,1984, US6150559,2000); (4) trimethylamine aqueous solution and dichloroethyl ether reaction, obtain bi-quaternary ammonium salt, gained bi-quaternary ammonium salt is except the residuum after desolventizing and dimethylamine reaction, dimethylamine is utilized to slough two methyl on bi-quaternary ammonium salt, obtain two (2-dimethylaminoethyl) ether of target product, productive rate 66%(US3400157,1968; US3426072,1969); (5) N, N '-Dimethylaminoethoxy sodium and N, N ' reaction of-dimethylamino monochloroethane, obtain two (2-dimethylaminoethyl) ether, obtain the productive rate (US3480675,1969) of 67%; (6) Trimethylamine 99 and dichloroethyl ether reaction, obtain bi-quaternary ammonium salt, gained bi-quaternary ammonium salt and four ethene triamines are 140 DEG C ~ 170 DEG C reactions, slough two methyl on bi-quaternary ammonium salt, obtain two (2-dimethylaminoethyl) ether of target product, productive rate 87%(US4625064,1986); (7) Trimethylamine 99 and dichloroethyl ether reaction, obtain bi-quaternary ammonium salt, gained bi-quaternary ammonium salt and diethylenetriamine are 145 DEG C ~ 155 DEG C reactions, slough two methyl on bi-quaternary ammonium salt, obtain two (2-dimethylaminoethyl) ether of target product, obtain the product of content more than 98% (CN1092082,1994).
In the preparation method of above-mentioned two (2-dimethylaminoethyl) ether, or need to carry out at high temperature under high pressure, severe reaction conditions; Or the aftertreatment of product is complicated, cost is higher; Or yield and the purity of product are undesirable.
Summary of the invention
A kind of method of coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether, comprising:
(1) mixture of Monomethylamine, dimethylamine and Trimethylamine 99 and two (2-halogenated ethyl) ether are reacted at least 2h between 30 DEG C ~ 100 DEG C;
(2) product step (1) obtained and polyethylene polyamine react at least 3h between 100 DEG C ~ 180 DEG C.
For reaction, the present invention is to Monomethylamine, in the mixture of dimethylamine and Trimethylamine 99, the ratio of three kinds of components has no particular limits, but in methylamine production, Monomethylamine, dimethylamine and Trimethylamine 99 mass ratio are generally 10 ~ 50:20 ~ 65:10 ~ 60, consider that an object of the present invention utilizes the mixture of the three kinds of methylamines obtained to come coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether, to avoid separation three kinds of methylamines, thus reduce facility investment and production cost, therefore in the present invention, Monomethylamine, the mass ratio of dimethylamine and Trimethylamine 99 is generally in above-mentioned proportional range.
Described two (2-halogenated ethyl) ethers are two (2-Chloroethyl) ether, two (2-bromoethyl) ether or two (2-iodoethyl) ethers.
Step preferably uses solvent in (1), after the reaction of step (1) terminates, is first separated except desolventizing, and then carries out the reaction of step (2) by the reaction product after desolventizing.Described solvent is selected from one or more in water methanol, ethanol, n-propyl alcohol and Virahol.
According to content disclosed by the invention, should be understood that the reaction of step (1) to react away the halogen atom in two (2-halogenated ethyl) ether, thus can the easily suitable proportion of reactant in determining step (1).Generally, the total mole number of Monomethylamine, dimethylamine and Trimethylamine 99 is 1 ~ 5:1 with the ratio of the mole number of two (2-halogenated ethyl) ether.
The temperature of reaction of step (1) is preferably 50 DEG C ~ 90 DEG C, and the reaction times is preferably 5h ~ 8h;
Described polyethylene polyamine is preferably one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
In step (2), in two (2-halogenated ethyl) the ether mole numbers in step (1) for 1, the consumption of polyamines polyene is 0.3 ~ 1.
The temperature of reaction of step (2) is preferably 120 DEG C ~ 160 DEG C, and the reaction times is preferably 6h ~ 12h;
The present invention passes through mixture and the reaction of two (2-halogenated ethyl) ether of Monomethylamine, dimethylamine and Trimethylamine 99, first N-methylmorpholine muriate is obtained, N, N '-dimethyl morpholine muriate and bi-quaternary ammonium salt, then products therefrom N-methylmorpholine muriate, N, N '-dimethyl morpholine muriate and bi-quaternary ammonium salt, demethylating under the effect of polyamines polyene, obtains N-methylmorpholine and two (2-dimethylaminoethyl) ether.
In method of the present invention, relate generally to following reaction:
Reaction process one:
Reaction process two:
Reaction process three:
Compared with prior art, the present invention has following characteristics:
The methylamine mixture that methyl alcohol and ammonia directly synthesize, do not need to be separated into Monomethylamine, dimethylamine and Trimethylamine 99, the mixture of methylamine is directly used as the substrate of reactant, decrease the sepn process of mixing methylamine, decrease the loss of sepn process, reduce facility investment, save cost and resource simultaneously.
Reaction under high pressure is not needed in the reaction process mixing methylamine and saturated dihalide, just can carry out smoothly under normal pressure, reduce facility investment, the N-methyl polyamines polyene generated can continue to methylate and generate many methyl polyethylene polyamine, such as N-methyl diethylenetriamine can continue to methylate and obtain pentamethyl-diethylenetriamine product, and this product is the whipping agent of polyurethanes product fine.
Embodiment
Further illustrate the present invention by the following examples.
Embodiment 1
By the Monomethylamine of mass content 40%, dimethylamine and trimethylamine aqueous solution 300g(Monomethylamine, the mass ratio 2:3:4 of dimethylamine and Trimethylamine 99) and dichloroethyl ether 200g to join in reaction flask in reaction, be warmed up to 70 DEG C of reaction 5 ~ 8h, generate N-methylmorpholine muriate, N, N '-dimethyl morpholine muriate and bi-quaternary ammonium salt, temperature is raised to 100 DEG C of decompressions and dewaters, products therefrom adds 180g diethylenetriamine in 2h, be warmed up to 160 DEG C and continue reaction 8 ~ 10h, obtain product N-methylmorpholine, two (2-dimethylaminoethyl) ether and N-methyl diethylenetriamine hydrochloride, leave standstill, separate supernatant liquid layer, liquid level underpressure distillation obtains N-methylmorpholine respectively, two (2-dimethylaminoethyl) ether, content is all more than 98%, overall yield 85%, remaining N-methyl diethylenetriamine is by adding the sodium hydroxide alkaline solution neutralization of massfraction 30%, or with formic acid and formaldehyde reaction, obtain polyurethane foams pentamethyl-diethylenetriamine.
Embodiment 2
By the Monomethylamine of mass content 40%, the ethanolic soln 300g(Monomethylamine of dimethylamine and Trimethylamine 99, the mass ratio of dimethylamine and Trimethylamine 99 is 1:1:1) and dichloroethyl ether 200g join in reaction flask and react, be warmed up to 70 DEG C of reaction 6h, generate N-methylmorpholine muriate, N, N '-dimethyl morpholine muriate and bi-quaternary ammonium salt, temperature is raised to 90 DEG C of removing ethanol, products therefrom adds 150g diethylenetriamine in 2h, be warmed up to 160 DEG C and continue reaction 8 ~ 10h, obtain product N-methylmorpholine, two (2-dimethylaminoethyl) ether and N-methyl diethylenetriamine hydrochloride, leave standstill, separate supernatant liquid layer, liquid level underpressure distillation obtains N-methylmorpholine respectively, two (2-dimethylaminoethyl) ether, content is all more than 98%, overall yield 91%, isolated lower floor solid layer N-methyl diethylenetriamine is by adding the sodium hydroxide alkaline solution neutralization of massfraction 30%, or with formic acid and formaldehyde reaction, obtain polyurethane foams pentamethyl-diethylenetriamine.
Embodiment 3
By the Monomethylamine of mass content 40%, the mixture methanol solution 300g(Monomethylamine of dimethylamine and Trimethylamine 99, the mass ratio of dimethylamine and Trimethylamine 99 is 1:2:2) and dichloroethyl ether 200g join in reaction flask and react, be warmed up to 50 DEG C of reaction 8h, generate N-methylmorpholine muriate, N, N '-dimethyl morpholine muriate and bi-quaternary ammonium salt, temperature is raised to 70 DEG C of removing methyl alcohol, products therefrom adds 200g triethylene tetramine in 2h, be warmed up to 160 DEG C of reaction 8 ~ 10h, obtain product N-methylmorpholine, two (2-dimethylaminoethyl) ether and N-methyl triethylene tetramine hydrochloride, leave standstill, separate supernatant liquid layer, liquid level underpressure distillation obtains N-methylmorpholine respectively, two (2-dimethylaminoethyl) ether, content is all more than 98%, overall yield 90%, the sodium hydroxide alkaline solution neutralization of isolated lower floor solid layer N-methyl triethylene tetramine by adding 30%, or with formic acid and formaldehyde reaction, obtain polyurethane foams pentamethyl-diethylenetriamine.
Claims (7)
1. the method for coproduction N-methylmorpholine and two (2-dimethylaminoethyl) ether, comprising:
(1) mixture of Monomethylamine, dimethylamine and Trimethylamine 99 and two (2-halogenated ethyl) ether are reacted at least 2h between 30 DEG C ~ 100 DEG C, in described Monomethylamine, dimethylamine and Trimethylamine 99 mixture, the mass ratio of Monomethylamine, dimethylamine and Trimethylamine 99 is 10 ~ 50:20 ~ 65:10 ~ 60; The total mole number of Monomethylamine, dimethylamine and Trimethylamine 99 is 1 ~ 5:1 with the ratio of the mole number of two (2-halogenated ethyl) ether;
(2) product step (1) obtained and polyethylene polyamine react at least 3h between 100 DEG C ~ 180 DEG C.
2. in accordance with the method for claim 1, it is characterized in that, described two (2-halogenated ethyl) ethers are two (2-Chloroethyl) ether, two (2-bromoethyl) ether or two (2-iodoethyl) ethers.
3. in accordance with the method for claim 1, it is characterized in that, use solvent in step (1), after the reaction of step (1) terminates, first be separated except desolventizing, and then carry out the reaction of step (2) by the reaction product after desolventizing; Described solvent is selected from one or more in water, methyl alcohol, ethanol, n-propyl alcohol and Virahol.
4. in accordance with the method for claim 1, it is characterized in that, the temperature of reaction of step (1) is 50 DEG C ~ 90 DEG C, and the reaction times is 5h ~ 8h.
5. in accordance with the method for claim 1, it is characterized in that, described polyethylene polyamine is one or more in diethylenetriamine, triethylene tetramine, tetraethylene pentamine and five ethene hexamines.
6. in accordance with the method for claim 1, it is characterized in that, in step (2), in two (2-halogenated ethyl) the ether mole numbers in step (1) for 1, the consumption of polyamines polyene is 0.3 ~ 1.
7. in accordance with the method for claim 1, it is characterized in that, the temperature of reaction of step (2) is 120 DEG C ~ 160 DEG C, and the reaction times is 6h ~ 12h.
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| CN103922945B (en) * | 2014-04-09 | 2015-07-08 | 四川之江高新材料股份有限公司 | Method for synthesizing bis(2-dialkyl aminoethyl)ether |
| CN114618390B (en) * | 2020-12-08 | 2024-02-20 | 江苏万盛大伟化学有限公司 | Fixed bed reactor for producing N-methylmorpholine by continuous method |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3155656A (en) * | 1960-04-14 | 1964-11-03 | Pennsalt Chemicals Corp | Novel process for nu-alkylmorpholines |
| US4625064A (en) * | 1983-04-07 | 1986-11-25 | Toyo Soda Manufacturing Co., Ltd. | Method for producing bis [β(N,N-dimethylamino)ethyl]ether |
| CN1092082A (en) * | 1993-03-10 | 1994-09-14 | 金坛县助剂厂 | The production method of two (2-dimethylamino ethyl) ether catalysts during polyurethane high-elastic foam plastic is produced |
| CN102452946A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of bi-(2-dimethylamino ethyl)ether |
-
2012
- 2012-08-27 CN CN201210307914.3A patent/CN103626721B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3155656A (en) * | 1960-04-14 | 1964-11-03 | Pennsalt Chemicals Corp | Novel process for nu-alkylmorpholines |
| US4625064A (en) * | 1983-04-07 | 1986-11-25 | Toyo Soda Manufacturing Co., Ltd. | Method for producing bis [β(N,N-dimethylamino)ethyl]ether |
| CN1092082A (en) * | 1993-03-10 | 1994-09-14 | 金坛县助剂厂 | The production method of two (2-dimethylamino ethyl) ether catalysts during polyurethane high-elastic foam plastic is produced |
| CN102452946A (en) * | 2010-10-25 | 2012-05-16 | 中国石油化工股份有限公司 | Preparation method of bi-(2-dimethylamino ethyl)ether |
Non-Patent Citations (1)
| Title |
|---|
| N-甲基吗啉合成工艺的研究;赵淑梅，等;《精细化工》;19990630;第16卷(第3期);第62-64页 * |
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